Preparation of aliphatic amines



Patented Dec. 10, 1946 I PREPARATION OF ALIPHATIC AIMINES Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application Apr-i122, 1943,

Serial No. 484,078

This invention relates to aliphatic hydro y amines and to the preparation thereof.

It is known that aliphatic monoamines can be prepared by condensing monohydric alcohols with ammonia, in the presence of a metallic hythe manner of practicing our invention. drogenation catalyst. When dihydric alcohols, such as tetramethylene glycol and pentamethyl- Example 2 EZJ ZZQZZ Q anon] ene glycol, are condensed with ammonia in the v presence of a hydrogenation catalyst, however, a 00 g. of methylene 8 3 0 considerable amount of cyclization occurs with 10 (HMMHPW the formation of compounds such as pyrrol and pyridine, so that tetramethylene diamine and I pentamethylene diamine cannot be commercialwere cmirged mto an autoclave with 20 of prepared by thiS method For thi season Raney nickel catalyst. The glycol was then satparently tetraand pentamethylene diamines, as mjated with ammoma from cyhnder of ammo well as high,3r molecular weight diamines, are mm. The autoclave was closed and the mixture prepared by reducing the appro riate dinit i1 I heated with shaking at 205 C. for 31 hours. The We have now f d that dihydnc ether a1co autoclave was then cooled and the contents made hols,' such as diethylene glycol and triethylene acid with hydrochlonc acid- T -M glycol, can he condensed with ammonia, in the terials were then removed from the mixture by presence of hydrogenation catalysts to give good distillation under reduced pressure. The residue yields of hydroxy amines. Some cyclization oc-. treated Wlth an excess of Percent aqueous curs and some formation of diamines occur, but Sodlum hydroxide 0 free the 9 bodies fmm the hydroxy amines can be readily separated their hydrochlorides. The amines which sepafr m the cyclic compounds and the dmminea 25 rated were removed from the aqueous liquors and We have also found that aliphatic diamines can dlsmled under redilced plessure- 8- 0f be prepared in good yields from hexato decat NH, meth lane 1 cols b condensin the l cols with 1 ammgnia, the piesence of hygrsggenation boiling at to C. at 5 mm. of mercury prescatalyst I so sure and 40 g. of

It is accordingly, an object of our inventioi; to HO-CzH4 OCzH4O-CzH4-NH: provide new hydroxy amines. A further ob ect o c is to provide a process for prepmng such boiling at .to 1 30 C. at 4 mm. of mercury pressure, were obtained. The residue from the droxy amines and a. process for, preparing didi tin ti 6 t i d m b m ec nd amines. Other objects will become apparent at s a on on a g er 0 n8 8 0 My hereinafter. and tertiary amines.

In accordance with our invention, we condense Example. 2.2-(2-hydro:ryethoxy)-eth1/lamine ammonia with a dihydric alcohol characterized by one of the following general formulas: 424 of diethylene glycol H2-CH2-O Heme an g.o nceon eseg rwerepace an autoclave. The mixture was saturated with wherein n represents a positive integer of from6 ammonia from a cylinder of ammonia. The auto 10 and :1: represents a positive integer of from toclave was then closed and the mixture was 1 to 2, at a temperature of from about C. to 45 heated at 205 C. with shaking for 37 hours. At about 400 C., in the presence of a hydrogenation the end of this time, the autoclave was cooled and catalyst. When diethylene glycol is employed as the contents made acid with hydrochloric acid. a starting material, the temperature employed is The monobasic materials were then removed advantageously from 200 to 250 C. Exemplary from the mixture by distillation under reduced of hydrogenation catalysts which w hav 50 pressure. To the residue was added an excess of ployed are Raney nickel, copper chromite, cop- 50 percent aqueous sodium hydroxide to free the per nickel chromite, iron, cobalt, titanium, copamino bodies from their hydrochlorides. The per, etc. The condensations can be carried out amines which separated were removed from the in the liquid or gaseous phase. If the condensaaqueous liquors and fractionally distilled, first at tions are carried out in the gaseous phase, the no ordinary pressures and then under reduced pres- 4Claims. (01. 260-584) 2 dihydric alcohol is led over the catalyst, e. g. nickel on kieselguhr, in a glass or metal tube heated to the desired temperature.

The following examples will serve to illustrate sures. Morpholine boiling at 182 to 184 C. at 745 mm. of mercury pressure, and a good yield of 2-(2-hydroxyethoxy)-ethylamine boiling at 123 C. at '1 mm. of mercury pressure, were obtained. In addition there was obtained a small amount of some amines boiling between 135 C. and 180 C. at '7 mm. of mercury pressure.

Example 3.-1,10-'didmino decane 82 g. of decamethylene glycol were placed in an autoclave with 10 g. of Raney nickel. To the mixture were added 180 g. of ammonia by passing ammonia into the mixture from a cylinder of ammonia; The autoclave was then closed and the mixture heated with shaking at 220 to 260 C. for 40 hours. The autoclave was then cooled and the contents steam distilled to obtain the decamethylene diamine. A 25 percent yield of diamine melting at 61 to 62 C. was obtained.

In a similar manner octamethylene glycol can be condensed with ammonia to give 1,8-diamino octane and hexamethylene glycol can be condensed with ammonia to give 1,6-diamino hexane.

What we claim as our invention and desire to be secured by Letters Patent of the United States is:

1. A process for preparing an aliphatic hydroxyamine comprising condensing ammonia at a temperature of from about 200 to about 250 C.,in the presence of a metallic hydrogenation catalyst.

3. A process for preparing a hydroxyamlne comprising condensing ammonia with a dihydric alcohol of the following formula:

CH:-O-CHz-CH2-OH I at a temperature of from about 200 to about 250 C., in the presence of a nickel hydrogenation catalyst.

4. 2- [2 (Z-hydroxyethoxy) ethoxyl-ethylamine.

JOSEPH B. DICKEY. JAMES G. McNALLY. 

